CN105764635B

CN105764635B - The method of gloss laminar structure is manufactured at low temperature

Info

Publication number: CN105764635B
Application number: CN201480063944.1A
Authority: CN
Inventors: S·贝尔; K-U·博尔特
Original assignee: Heraeus Precious Metals GmbH and Co KG
Current assignee: Heraeus Deutschland GmbH and Co KG
Priority date: 2013-09-24
Filing date: 2014-09-24
Publication date: 2019-11-12
Anticipated expiration: 2034-09-24
Also published as: JP2017501015A; US20160236280A1; EP3049202A1; KR20160060135A; US10384266B2; WO2015044189A1; CN105764635A; JP6667433B2

Abstract

The method for manufacturing layer structure (2), it includes following steps: E1) a kind of composition (6) is provided, it includes gold (Au) particles of the amount of i) 0.1 to 50 weight %；Ii) it is supplemented to the polar protic organic solvent of 100 weight %；Iii it) is less than the water of 5 weight %, wherein these weight % based on the gross mass of composition (6) adds up to 100 weight % in each case；E2) composition (6) is applied on substrate (4) to generate precursor (12)；E3 precursor (12)) is heated to 25 to 200 DEG C of temperature to generate layer structure (2).

Description

The method of gloss laminar structure is manufactured at low temperature

The present invention relates to a kind of methods for manufacturing layer structure, and it includes following steps: E1. provides a kind of composition, Comprising i.0.1 to the golden Au particle of the amount of 50 weight %；Ii. it is supplemented to the polar protic organic solvent of 100 weight %；Iii. few In the water of 5 weight %, wherein these weight % based on the gross mass of the composition adds up to 100 weights in each case Measure %；E2. it applies the composition in substrate to generate precursor；E3., the precursor is heated to 25 to 200 DEG C of temperature To generate the layer structure of coating.

The invention further relates to by the step E1. and E2. of the above method layer structure precursor obtained and can pass through The layer structure that the above method obtains.

In addition, the present invention provides a kind of composition, and it includes: z1. is based on the gross mass 0.1 of the composition to 50Au weight Measure gold (Au) particle of the amount of %；Z2. the water of 0 to the 5 weight % of gross mass based on the composition；Z3. it is based on the combination The gross mass meter of object is supplemented to the polar protic organic solvent of 100 weight %.The present invention also provides include stratiform knot of the invention The object of structure or the layer structure that can be obtained by means of the present invention.

It is well known in the prior art for manufacturing the method for metal layer on the ceramic material.Therefore, in WO00/10941A1, The aqueous solution of mercaptan gold compound is applied on ceramics to realize polychromy by heating.Herein at 400 to 1200 DEG C At a temperature of heated.

The prior art does not describe for gold particle to be applied in substrate and forms any of bright layer gold by low temperature by it Possible mode.

In general, currently invention addresses at least partly overcome the problems, such as the prior art.

It is having in mind another problem is that the gold particle in substrate is converted to bright layer at low temperature.

In addition, a problem having in mind is to provide effective inexpensive method for manufacturing the layer structure comprising layer gold.

It is having in mind another problem is that providing the very environmentally friendly method for manufacturing layer structure.

In addition, a problem having in mind is the stratiform knot for being capable of providing the layer gold that can change in a wide range with its thickness Structure.

In addition, a problem having in mind is to provide the side of the layer structure for manufacturing the gold plating with pole firm attachment Method.

It is having in mind another problem is that the layer structure with pole glossy surface can be manufactured.

In addition, a problem having in mind be to provide can be used for being formed at low temperature layer gold, contain gold particle in a solvent Composition.

Present invention firstly provides a kind of methods for manufacturing layer structure, and it includes following steps:

E1., a kind of composition is provided, it includes

I.0.1 to gold (Au) particle of the amount of 50 weight %；

Ii. it is supplemented to the polar protic organic solvent of 100 weight %；

Iii. it is less than the water of 5 weight %,

Wherein these weight % in each case based on the gross mass of the composition adds up to 100 weight %；

E2. it applies the composition in substrate to generate precursor；

E3. the precursor is heated to 25 to 300 DEG C, preferably 25 to 250 DEG C, particularly preferred 25 to 200 DEG C of temperature, with Generate layer structure.

The offer of composition in step E1. can be the composition provided for this method with those skilled in the art And any mode selected carries out.The composition is preferably provided in the container for applying the composition among step E2. In addition, the container is preferably the container for the valve for having for measuring discharge the composition.

The composition includes 0.1 to 50 weight %, preferably 0.5 to 40 weight based on the gross mass of the composition Measure %, or golden (Au) particle of amount of preferably 1 to 20 weight %.In addition, the composition includes total matter based on the composition Meter is less than 5 weight %, preferably less than 4 weight %, or the water of preferably less than 3 weight %.The composition can additionally comprise to A kind of few annexing ingredient.

The composition includes based on the gross mass of the composition, and the polar protic for being supplemented to 100 weight % is organic Solvent, wherein these weight % based on the gross mass of the composition adds up to 100 weight % in each case.The pole Property proton-organic solvent can be those skilled in the art for this method any polar protic organic solvent.To the present invention Speech, proton solvent, which contains, to be bonded on property element more negatively and is therefore easy the hydrogen atom left.The polar protic organic solvent It is preferred that having 2 to 20 carbon atoms.In addition, the polar protic organic solvent have at least one polar protic group, such as-OH ,- SH、-NH、-NH₂,-COOH.The representative instance of polar protic organic solvent is alcohol, (for the purpose of the present invention, amine is aliphatic series and rouge to amine Ring race amine), amide and carboxylic acid.It is preferred here that lower alcohol, especially for example methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol and 2- methyl-2-propanol, methoxypropanol, ethyoxyl propyl alcohol, methyl cellosolve, ethyoxyl second Alcohol, 4- hydroxymethyl -1,3-dioxolane, preferably methanol, ethyl alcohol, propyl alcohol, butanol or in which at least two mixture.

In addition, the polar protic organic solvent can be selected from the mixing of glycol, amine, amide and carboxylic acid and wherein at least two kinds Object.The glycol can be selected from 1,2- ethylene glycol, 1,2- propylene glycol, 1,2,3- glycerine (glycerol), 1,2- butanediol, 1,3- fourth two Alcohol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, with The monosaccharide or disaccharides of liquid polyol mixing, 2,2- dimethyl propylene -1,3- glycol, preferably have 1,1,1- tri- (methylol) propane There are the polyethylene glycol of 3 to 500 repetitive units, such as mono- 1,2-PD, two -1,2-PDs, 1,2- butanediol, 2,3- Butanediol and wherein at least two kinds of mixture.The amine can be selected from ammonia, methylamine, ethamine, n-propylamine, isopropylamine, n-butylamine, diformazan Amine, diethylamine, two-n-propylamines, two-n-butylamines, pyrrolidines, piperidines, piperazine, N- thyl-piperazin, n-ethylpiperazine, morpholine, second Diamines, 1,2- propane diamine, 1,3- propane diamine, two (2- cyanoethyl) amine, two (2- amino-ethyl) amine, three (2- amino-ethyl) amine, Ethanol amine, diethanol amine, triethanolamine, Propanolamine, dipropanolamine and tripropanol amine and wherein at least two kinds of mixture.The acyl Amine can be selected from formamide, acetamide, propionamide, butyramide, pentanamide, caproamide, heptamide, caprylamide and wherein at least two kinds Mixture.The carboxylic acid can be selected from formic acid, acetic acid, acrylic acid, oxalic acid, citric acid, benzoic acid, niacin, succinic acid, maleic acid, Salicylic acid and wherein at least two kinds of mixture.Pointed alcohol is preferred.

Outside polar proton-organic solvent, the composition is preferably also comprising at least one additional aprotic solvent.The non-matter The optional ketone of sub- solvent, aldehyde and sulfoxide and wherein at least two kinds of mixture.The ketone can be selected from ethylene carbonate, N- crassitude Ketone, N- ethyl pyrrolidone, cyclohexanone.The aldehyde can be selected from formaldehyde, acetaldehyde, propionic aldehyde, octanal and wherein at least two kinds of mixture. The sulfoxide can be such as dimethyl sulfoxide.The composition preferably comprise based on the gross mass of the composition 0.1 to 10 weight %, Or the aprotic solvent of preferably 0.2 to 9 weight %, 0.5 to 5 weight %.

The composition being applied in substrate to generate precursor can be to apply in this approach with those skilled in the art Any mode for adding the composition and selecting carries out.Here, the substrate, hereinafter also referred to as basal layer, preferably at least part is by this Composition covering.

The application is preferably to deposit the composition or impregnates the combination of (dip) into the composition or both.Pass through deposition Apply the composition can for example by spin coating, dipping, casting, dropwise addition, spray, spray, blade coating, japanning (painting) Or printing carries out, such as by metering pump or ink jet printing, silk-screen printing, intaglio printing, hectographic printing or bat printing to basal layer On.The composition is applied on basal layer preferably by metering pump, ink jet printing, silk-screen printing or intaglio printing.The combination Object is preferably applied preferably with 0.01 micron to 250 microns of wet-film thickness with 0.1 micron to 50 microns of wet-film thickness.

For the purpose of the present invention, deposition, which refers to, will be used for the composition of application (preferably by the auxiliary tool of form of nozzle Referred to as liquid or printing composition) it is applied on surface to be covered.This can be carried out by various auxiliary tools.Therefore, it uses It can be deposited on basal layer through nozzle spray or injection or by slot die in the printing composition for applying or covering.In addition Method be act formula casting (curtain casting) and a spin coating.In addition, the printing composition for applying or covering can example Such as applies by roller or roller or be printed on substrate surface.Known spraying or gunite is micro- metering for example by nozzle Or digital printing.Here, the printing composition or will be used to apply through nozzle that (express) is used to apply or cover can be squeezed out Printing composition be simply added drop-wise on surface.

As another print process, it is preferable to use silk screen print method.In silk screen print method, by the material highly stable by size Material, such as timber；Metal, preferred steel；Ceramics or polymer constitute and have the wire mesh arrangement of selected mesh size to be covered Above object (substrate in this case).The printing composition for being used to apply or cover is applied to this silk through nozzle On the net and mesh is pressed through by scraper.Here, can apply in different location different amounts of for applying due to the pattern in silk screen The printing composition for adding or covering.Therefore, according to the geometry of mesh and arrangement, the printing composition for covering can be applied Uniform film, or completely or nearly without being used for the region of the printing composition of application and there is the print couple for being largely used to apply Close the region alternating of object.It is preferred that the uniform film for the printing composition for being used to cover is applied to surface.The mesh of silk screen The material (duplicating layer, screen printing template) that can be suitably applied is partially enclosed so that the printing composition is only in specified region It is transferred in substrate in (wherein mesh is open) to obtain such as specified structure, such as pattern.In addition it is also possible to using having The film (template) of specified aperture replaces silk screen to be covered with the printing composition.

According to the viscosity and polarity of the construction and the composition for covering of nozzle or roller or roller, can will have not The layer of stack pile is applied on the required surface of basal layer.The layer applied in application or covering preferably with 0.5 to 100 micron, It is preferred that 1 to 50 micron, particularly preferred 2 to 30 microns of thickness applies.The thickness of the layer of application is hereinbelow referred to as wet layer thickness. Wet layer thickness depends on the respective material applied in overwrite procedure.Measure wet layer thickness immediately after covering step.

In immersion, surface to be coated is for example pulled through to the bath of the composition comprising being used to apply.Alternatively, as in dip-coating As doing, which can also simply be immersed in the composition for being used for applying and be further taken out.It can be with during application The different-thickness of coating is realized by repeatedly impregnating.In addition, being as previously mentioned, coating layer thickness depends on the composition for application Selection.It may be implemented 0.5 to 100 micron, preferably 1 to 50 micron during application as a result, particularly preferred 2 to 30 microns Respective coating wet layer thickness.Also the combination of deposition and infusion method can be used.

In one embodiment, via the application well provided on layer to be covered, such as the respective surface of substrate The application of (application orifice) realization composition therefor.Here, the application well is preferably via the combination for application Object is joined on the surface.The special properties of this method (also referred to as micro- metering (micrometering)) are that it can be with The coating to be applied of different-thickness is applied to object by plain mode, on substrate surface.The application well can have any possibility Shape and size.The application well can be for example with the shape for being selected from round, oval, angular and star and combinations thereof.It should Application well can have 10 square nanometers to 1 square millimeter, and for preferably 100 square nanometers to 0.5 square millimeter, particularly preferred 100 is flat Square nanometer to 100 square microns area.Preferably by 2000 to 10000 millibars, preferably 2500 to 5000 millibars, particularly preferably The composition for being used to apply is applied to the surface through nozzle by 3000 to 4000 millibars of pressure.For covering composition with The engagement of substrate surface can be detached from surface during application to avoid the composition for application.It may thereby be ensured that by non- Often uniform film is applied on the surface.

The application of the composition is carried out preferably by silk screen print method or gravure printing method.One in this method is preferred real It applies in scheme, applies the composition via silk screen or by printing cylinder in printing process.The silk screen preferably comprise by steel or The frame that stainless steel is constituted.It is preferred that by also, it is preferred that the sieve or wire mesh arrangement being made of stainless steel wire or high strength synthetic fibre In the frame.

In a preferred embodiment of this method, which has 1 to 300 micron, preferably 2 to 200 microns or excellent Select 3 to 90 microns of mesh size.This is equivalent to about 70 to 635 mesh or about 100 to 600 mesh or about in each case The mesh number of 200 to 500 mesh, wherein unit mesh is equivalent to the screen density or every 2.54 centimetres of screen density of per inch.By silk In the case that wire mark brush applies, any business scraper can be used as scraper.The scraper preferably comprises polymer.The scraper is excellent Select the scraper hardness with 40 to 80Shore A.The composition preferably have 500 to 100000mPa*s, or preferably 700 to The viscosity of 50000mPa*s.

The substrate, which can have, allows the composition to be applied to any shape in substrate.The substrate preferably has at least one Continuous surface.At least one described continuous surface preferably has 1 square millimeter to 10 square metres, or preferably 10 square millimeters to 5 Square metre, or preferably 100 square millimeters to 1 square metre of area.The substrate can have round, annular, angular, conical or ellipse Circular structure.The shape of the substrate is preferably selected from sphere；Cone；Circle；It is polygon shaped like triangle, square, rectangle, it is trapezoidal, five Side shape, hexagon, heptagon or octagon；Ellipse and wherein at least two kinds of combination.Total continuous surface based on the substrate Product meter, during application in step E2, which is preferably covered by the composition to 5 to 100% degree, or preferably extremely 10 to 100% degree, or preferably to 15 to 100% degree.It can apply on the whole table area of substrate or according to pattern The composition.The region covered by the composition in substrate can replace with unlapped region as a result,.The pattern can have Rule construct, such as checkerboard pattern, honeycomb pattern or argyle design.Alternatively or additionally, the composition can be with irregular Pattern is applied in substrate.

After applying the composition in step E2. to generate precursor, the precursor is heated to 25 to 200 in step E3 DEG C, preferably 40 to 180 DEG C, or preferably 50 to 150 DEG C of temperature.Can with those skilled in the art can thus purposes selection appoint Where formula carry out precursor heating.The heating is preferably by selected from irradiation, baking oven heating, hot gas heating and wherein at least two The combined method heating of kind.For example it can implement to irradiate by infra-red radiation, laser emission, ultraviolet radioactive or combinations thereof.In Heating in baking oven, such as hot-air oven can be for example discontinuous or be carried out continuously.Hot gas heating can be by making hot gas Stream, as or mixtures thereof air, nitrogen, oxygen are carried out by the composition applied.The duration of heat in step E3. is excellent It is selected as 0.5 to 10 hour, or preferably 0.5 to 5 hour, or preferably 0.5 to 3 hour.The heating generates comprising at least substrate and contains The layer structure of layer gold (hereinafter also referred to as layer gold).

In a preferred embodiment of this method, gold particle have 2 to 25 nanometers, preferably 3 to 20 nanometers, or preferably 4 to 18 nanometers of diameter.For current applications, the diameter of gold particle is the average diameter of particle.It can be by the mixture The diameter of microexamination measurement gold particle.In order to accurately measure the size, two points farthest from one another on particle Draw imaginary circle.The void diameter of a circle is equivalent to the diameter of particle.The gold particle preferably has round to ellipse.Gold (Au) grain Son preferably has 20 nanometers, or preferably 15 nanometers, or preferably 12 nanometers of size distribution D₅₀, it means that not more than 50% grain Son is greater than designated diameter.Various method measurement granularities can be used.Preferably by laser light scattering, optical microscopy, single-particle Optical counting or in which at least two combination measure granularity.Furthermore it is preferred that being recorded by means of transmission electron microscopy (TEM) The optics individual assessment of image carry out the measurement of granularity and size distribution.

In a preferred embodiment of this method, in the range of 1 to 100000mPas, preferably 10 to In the range of 90000mPas, or the viscosity of the composition is preferably selected in the range of 20 to 50000mPas.1/500s's Viscosity is measured under shearing range.

In a preferred embodiment of this method, which includes the polynary of at least 20 weight % Alcohol.The polyalcohol is the organic compound at least two alcohol groups.The polyalcohol preferably has 2 to 10 alcohol groups.It should Polyalcohol can have other functional groups.At least one other functional group can be selected from-S-,-SH ,-O-,-OOH ,=O ,-N-,- NH、–NH₂、–P、–P(OH)₃,-Cl ,-F ,-Br and wherein at least two kinds of combination.

In a preferred embodiment of this method, which has 2 to 20 carbon atoms.

In a preferred embodiment of this method, which is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- third Glycol, 1,2,3- glycerine (glycerol), 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- fourth Triol, 1,2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1, 4- dihydroxy -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, 1,1, 1- tri- (methylol) propane, 2,2- dimethyl propylene -1,3- glycol, the polyethylene glycol preferably with 3 to 500 repetitive units and its In at least two mixture.

In a preferred embodiment of this method, the composition further includes sulfydryl-carboxyl chemical combination of logical formula (I) Object

SH-R₁-COOH (I)

Wherein

R₁It is substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀Alkyl,

Or at least one salt of this sulfydryl-carboxyl compound.

In a preferred embodiment of this method, the substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀Alkyl has at least one, preferably two or all following properties:

E1. the C₁-C₂₀At least one carbon atom of alkyl is former by least one nitrogen-atoms, oxygen atom, phosphorus atoms, sulphur Son, hydroxyl, carboxyl, halide, amine, amide, phosphate, sulfate or in which at least two combination replacement；Or

E2. the C₁-C₂₀Alkyl can be by the C of other substitution, unsubstituted, branching or non-branching₁-C₂₀Alkyl replaces or branch Change；Or

E3. the C₁-C₂₀At least one carbon atom of alkyl is by aryl substitution or in the feelings of 5-, 6- or 7- member hetero-aromatic ring Under condition by 1,2,3 or 4 nitrogen, oxygen and sulphur atom substitute, wherein the heteroaryl can by halogen atom, hydroxyl, nitro, amino, by Amino, cyano, trifluoromethyl, the alkyl with 1 to 4 carbon atom, the alkoxy with 1 to 4 carbon atom of protection replace.

For the purpose of the present invention, unsubstituted C₁-C₂₀Alkyl is by 1 to 20-CH₂Or the alkyl that-CH- group is constituted. For the purpose of the present invention, substituted C₁-C₂₀Alkyl is by 1 to 20-CH₂Group constitutes and wherein at least one-CH₂Or-CH- The alkyl that H atom on group has been substituted by another atom or another atomic group.Another atom can be selected from carbon atom, nitrogen-atoms, Oxygen atom, phosphorus atoms, sulphur atom, halogen (halide) and wherein at least two kinds of combination.Another atomic group can be selected from replacing hydrocarbon Base, unsubstituting hydrocarbyl, branched hydrocarbyl radical, non-branching alkyl, saturated hydrocarbyl, unsaturated alkyl, cyclic hydrocarbon radical, multi-ring alkyl, aryl, Non-aromatic alkyl, acyl group, hydroxyl, carboxyl, primary amine, secondary amine, tertiary amine, amide, phosphate, sulfate, sulfonic group, mercapto and wherein At least two combination.

For the purpose of the present invention, non-branching C₁-C₂₀Alkyl is by 1 to 20-CH₂Or the straight-chain hydrocarbons that-CH- group is constituted Base.Branching C₁-C₂₀Alkyl is by 1 to 20-CH₂Or-CH- group constitutes and wherein at least one-CH₂Or on-CH- group The alkyl that has been substituted by another alkyl of H atom.This another alkyl equally can be substituted or unsubstituted and branching or non- Branching it is cyclic annular or polycyclic.

For the purpose of the present invention, cyclic annular C₁-C₂₀Alkyl is by 1 to 20-CH₂Or-CH- group constitutes and wherein carbon atom The alkyl being arranged in ring.Polycyclic C₁-C₂₀Alkyl is by 1 to 20-CH₂Or-CH- group constitutes and wherein carbon atom is cyclic The alkyl being arranged in two or more rings.Cyclic annular and multi-ring alkyl can also have aromatic ring.

The substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀Alkyl can have one of following combination In the property mentioned:

L1. replace C₁-C₂₀Alkyl；

L2. unsubstituted C₁-C₂₀Alkyl；

L3. the branching C replaced₁-C₂₀Alkyl；

L4. the non-branching C replaced₁-C₂₀Alkyl；

L5. unsubstituted branching C₁-C₂₀Alkyl；

L6. unsubstituted non-branching C₁-C₂₀Alkyl；

L7. substitution, branching, cricoid C₁-C₂₀Alkyl；

L8. substitution, non-branching, cricoid C₁-C₂₀Alkyl；

L9. unsubstituted, branching, cricoid C₁-C₂₀Alkyl；

L10. unsubstituted, non-branching, cricoid C₁-C₂₀Alkyl；

L11. substitution, branching, polycyclic C₁-C₂₀Alkyl；

L12. substitution, non-branching, polycyclic C₁-C₂₀Alkyl；

L13. unsubstituted, branching, polycyclic C₁-C₂₀Alkyl；

L14. unsubstituted, non-branching, polycyclic C₁-C₂₀Alkyl.

It is as previously mentioned, substituted hydrocarbon radical can also have above-mentioned property or combination of properties again.

In a preferred embodiment of this method, the composition includes 0.1 to 4 based on the gross mass of the composition Weight %, preferably 0.5 to 3.5 weight %, or sulfydryl-carboxyl compound of preferably 0.3 to 3.0 weight %.

In a preferred embodiment of this method, which is selected from L-cysteine, half Guang ammonia of D- Acid, γ-L- glutamy-L- cysteinyl glycine (glutathione), (sulphur is general for glycine by (RS)-N- (2- sulfydryl -1- oxygen propyl group) Luo Ning), mercapto succinic acid, n-acetylcysteine, thiosalicylic acid, dimercaptosuccinic acid, l-methionine, D- first sulphur ammonia Acid, thiocarbamide, 2 mercaptopropionic acid, thioglycerol, thio-2 acid, cystine, 3- mercapto-propionate, sodium thioglycolate (Na ) and wherein at least two kinds of mixture thioglycolate.

In a preferred embodiment of this method, the composition includes to be selected from silver (Ag), platinum (Pt), palladium (Pd), copper (Cu), at least one additional metal of rhodium (Rh) and wherein at least two kinds of combination.At least one additional metal can be used as Metallic exists as additional metal-organic complex.The composition preferably comprises based on the gross mass of the composition 0.1 to 5 weight %, or preferably 0.2 to 4.5 weight %, or the additional metal of preferably 0.5 to 4 weight %.

The organic component of the metal-organic complex preferably comprise at least one, at least two or more carbon it is former Son, preferably 2 to 100, or preferably 4 to 50, or the molecule of preferably 5 to 20 carbon atoms.The organic component preferably comprise one or The non-metallic atom of two or more non-carbon.At least one of at least one non-metallic atom further preferably organises with this Close the metal component at least Coordination interaction of object, preferred ion interaction.Can also at least one non-metallic atom with Covalent bond is formed between the metal component.The non-metallic atom is preferably selected from oxygen, sulphur, nitrogen, phosphorus, silicon, halogen and wherein at least two The mixture of kind.At least one described carbon atom in the organic component of the metal organic compound with described at least one is non- Metallic atom is preferably formed as organic compound together.

In a preferred embodiment of this method, the metal organic compound have selected from carbonic ester, oxalate, Ester, carboxylate, halogenated carboxylic ester, hydroxycarboxylic acid esters, pyruvate, keto ester (ketonate), phosphate, phosphite ester, phosphorus Compound, phosphine, sulphonic acid ester and sulphonic resin acid esters and wherein at least two kinds of mixture organic component.The organic component is preferred Selected from acetic acid esters, propionic ester, butyrate, isobutyrate, ethyl butyric acid ester, valerate, capronate, heptanoate, caprylate, different pungent Acid esters, pelargonate, decylate, isononoate, pivalate, cyclohexane butyric acid ester, acetylacetonate, ethyl hexanoate, hydroxyl Propionic ester, trifluoro-acetate, hexafluoro -2,4- pentanedione acid esters (pentadionate)；Neodecanoic acid ester, methanesulfonates, ethanesulfonic acid The unsaturated natural and/or synthetic resin of ester, propane sulfonic acid ester, triflate, p-methyl benzenesulfonic acid ester, benzene sulfonate, sulfur-bearing, example Such as turpentine oil, rosin and copaiba balsam and wherein at least two kinds of mixture.

It is as previously mentioned, the composition can be in addition to the above components also comprising at least one annexing ingredient.Described at least one Kind annexing ingredient is preferably selected from adhesive, added solvent, crosslinking agent, another additive and wherein at least two kinds of mixture.Make For adhesive, such as polyurethane, polyacrylate, polyester, polyvinyl alcohol, polysulfones and wherein at least two kinds of mixing can be used Object.The added solvent is preferably selected from dimethyl sulfoxide (DMSO), ethylene glycol, n-methyl-2-pyrrolidone (NMP), ammonia, alcohol such as second Alcohol, isopropanol or hexanol, ethoxy ethanol, methyl cellosolve, methoxypropanol, ethoxy ethanol and wherein at least two kinds mixed Close object.The crosslinking agent may, for example, be silane.The additional additives can be selected from nonionic surfactant, such as polyalkylene glycol ether Or alkyl polyglucoside, ionic surface active agent, such as alkyl carboxylate, alkylbenzene sulfonate or paraffin sulfonate and wherein at least Two kinds of mixture.The composition preferably comprises 0.1 to 5 weight %, preferably 0.5 to 4.5 based on the gross mass of the composition Weight %, or at least one annexing ingredient of preferably 1 to 4 weight %.

In a preferred embodiment of this method, the composition has 3 to 8, or preferably 4 to 7 pH.

In a preferred embodiment of this method, the composition further includes surface reactive material.The composition Preferably comprise 0.001 to 5 weight %, preferably 0.005 to 4 weight %, or the surface reactive material of preferably 0.01 to 3 weight %. The surface reactive material can be selected from nonionic surfactant, anionic surfactant, cationic surfactant and both sexes Surfactant and wherein at least two kinds of mixture.The all surface activating agent mentioned includes nonpolar moiety and polarity portion Point.Nonpolar moiety can be selected from alkyl, alkylbenzene group and combinations thereof.The polar portion of nonionic surfactant can be selected from alcohol Group, ether group, acrylate group and wherein at least two kinds of combination.The polar portion of anionic surfactant can be selected from Carboxylate radical, sulfonate radical, sulfate radical and wherein at least two kinds of mixture.The polar portion of cationic surfactant can be such as It is quaternary ammonium group.The polar portion of amphoteric surfactant can be selected from cationic surfactant and anionic surfactant The combination of at least one polar portion.The surface reactive material further preferably includes silicon-containing compound.One reality of such compound Example is two of the molal weight with 400 to 10000g/mol, preferably 500 to 9000g/mol, or preferably 600 to 8000g/mol Methyl polysiloxane.The example of commercial surface biologically active prod is polyether-modified dimethyl silicone polymer, such as BYK- Polyacrylate, such as BYK-And polypropylene glycol, such as DISPERBYK-All available from Byk-Chemie GmbH in Wesel。

In a preferred embodiment of this method, in additional step E4 at least in a part of the layer structure Apply protective layer.The protective layer is preferably selected from physical dryness type surface covering, oxidation cross-linked surface covering, heat cross-linking surface covering (such as business clear coat of motor vehicle) and crosslinking with radiation surface covering.

The substrate that the composition is applied to as described above can be those skilled in the art and be used in manufacture layer structure Any material.In a preferred embodiment of this method, which is selected from paper, timber, fabric, glass, polymer, gold Belong to, ceramics, keratinization layer, especially finger nail or toenail, and wherein at least two kinds of combination.The paper can be this field skill Art personnel can be any kind of paper of the choice of the substrates in this method.The paper preferably has 10 to 500 grams/m or excellent Select 20 to 400 grams/m, or preferably 50 to 350 grams/m of per unit area weight.Timber can be this field skill Art personnel can be any type and form of timber of the choice of the substrates in this method.

The fabric, which can be those skilled in the art, to be any fabric of the choice of the substrates in layer structure.The fabric can In the form of being fiber, woven fabric or non-woven fabric.The fabric can be woven, braiding, lopping (loop), knitting or non-woven 's.The fabric may include that can preferably be made of natural material, such as wool, cotton, silk, cellulose or other natural fibers.This is knitted Object also may include, preferably can also be by synthetic material, such as nylon, polyester, polyacrylic acid, polyacrylonitrile, polyamide, Nomex Or fiber or carbon, the glass or metallic fiber (line) of other polymer are constituted.The fabric also may include, preferably can also be by least The mixture of two kinds of materials is constituted.

The glass, which can be those skilled in the art, to be any glass of the choice of the substrates in layer structure.The glass is excellent Choosing is selected from alkali glass, alkali-free glass, silicate glass and wherein at least two kinds of mixture.The glass is preferably selected from sodium calcium glass Glass, lead-alkali glass, borosilicate glass, alumina silicate glass, quartz glass and wherein at least two kinds of mixture.

The polymer, which can be those skilled in the art, to be any polymer of the choice of the substrates in layer structure.This is poly- It closes object and is preferably selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polyvinylpyrrolidone, polychlorostyrene Ethylene, polyvinyl acetate, poly- vinyl butyrate, polyacrylate, polyacrylamide, polymethacrylates, poly- methyl-prop Acrylamide, polyacrylonitrile, copolymer in cinnamic acrylic ester, vinyl acetate/acrylate copolymer and ethylene/acetic acid second Enoate copolymer, polybutadiene, polyisoprene, polystyrene, polyethers, polyester, polycarbonate, polyurethane, polyamide, polyamides Imines, polysulfones, melamine formaldehyde resin, epoxy resin, silicone resin and wherein at least two kinds of mixture.

The metal, which can be those skilled in the art, to be any metal of the choice of the substrates in layer structure.The metal is excellent Choosing is selected from iron, steel, aluminium, silver, titanium, copper, gold, tin, zinc, lead, silicon and wherein at least two kinds of mixture or combination.

The ceramics, which can be those skilled in the art, to be any ceramic material of the choice of the substrates in layer structure.The pottery Porcelain is preferably selected from oxide ceramics, silicate ceramics, non-oxide ceramics and wherein at least two kinds of mixture.

The oxide ceramics is preferably selected from metal oxide, half-metal oxide and its mixture.The metal oxide Metal can be selected from aluminium, beryllium, barium, boron, calcium, magnesium, sodium, potassium, iron, zirconium, titanium and wherein at least two kinds of mixture.The metal oxide It is preferably selected from aluminium oxide (Al₂O₃), sodium oxide molybdena, boron oxide, calcium oxide, magnesia (MgO), silica (SiO₂), zirconium oxide (ZrO₂), yttrium oxide (Y₂O₃), aluminium titanates (Al₂TiO₅) and wherein at least two kinds of mixture.Half gold medal of the half-metal oxide Category is preferably selected from boron, silicon, arsenic, tellurium and wherein at least two kinds of mixture.

The silicate ceramics is preferably selected from talcum (Mg₃[Si₄O₁₀(OH)₂]), cordierite ((Mg, Fe²⁺)₂(Al₂Si) [Al₂Si₄O₁₈]), mullite (Al₂Al_2+2xSi_2-2xO_10-x, the wherein Lacking oxygen number of the every structure cell of x=), feldspar ((Ba, Ca, Na,K,NH₄)(Al,B,Si)₄O₈) and wherein at least two kinds of mixture.The silicate ceramics is preferably porcelain.

The non-oxide ceramics can be selected from carbide, nitride and its mixture.The carbide can be selected from silicon carbide (SiC), boron carbide (B₄C), titanium carbide (TiC), tungsten carbide, cementite (Fe₃C).The nitride can be selected from silicon nitride (Si₃N₄)、 Aluminium nitride (AlN), silicon-aluminium-nitride-oxide (SIALON) and wherein at least two kinds of mixture.

In a preferred embodiment of this method, which has less than 10¹³The conductivity of S/cm.The substrate is preferred With 10³S/cm to 10^-13S/cm, or preferably 10²S/cm to 10^-10S/cm or 10¹S/cm to 10^-8The conductivity of S/cm.

In a preferred embodiment of this method, the application of the composition in step E2. is by brush, silk screen, felt Pen (felt pen), fountain pen (fountain pen) or nozzle carry out.As brush, those skilled in the art can be used Meeting any conventional brush that purposes selects thus.The selection and size of silk screen and nozzle are had indicated that above.

The present invention also provides the layer structure precursors that can be obtained by the processing step E1 and E2 of the above method.

In a preferred embodiment of the precursor, which has at least one following property:

V1.0.1 millimeters to 5 centimetres of substrate thickness；

V2.0.1 microns to 70 microns, preferably 0.1 to 10 micron, or preferably 0.1 to 1 micron apply in step E2. Composition thickness；

V3. less than 10¹³The substrate conductivity of S/cm；

V4.10^-1S/cm to 10^-8The conductivity for the composition of S/cm applied in step E2..

The present invention also provides the layer structures that can be obtained by the above method.

In a preferred embodiment of the layer structure, which has at least one following property:

S1. the gold of the thickness in the layer structure comprising at least gold of 70 weight % and with 0.05 micron to 1 micron Belong to layer；

S2. less than 10¹³The conductivity of S/cm；

The glossiness of S3.500 to 1300GU；

S4.10 to 20kg/l；It is preferred that 12 to 19.6kg/l, or preferably 15 to 19.4kg/l density.

The present invention also provides a kind of composition, it includes:

Gold (Au) particle of the amount of z1.0.1 to 50 weight %；

The water of z2.0 to 5 weight %；

Z3. it is supplemented to the polar protic organic solvent of 100 weight %；

Wherein these weight % in each case based on the gross mass of the composition adds up to 100 weight %.

In a preferred embodiment of the composition, the composition includes to add group selected from following at least one Point, preferably two kinds of annexing ingredients, or preferably all annexing ingredients:

Z4. based on the gross mass of the composition, the polyvinylpyrrolidone of the amount of 0 to 10 weight %；

Z5. based on the gross mass of the composition, the polyalcohol of the amount of 0 to 90 weight %.

In a preferred embodiment of the composition, the polyalcohol be selected from 1,2- ethylene glycol, 1,2-PD, 1,2, 3- glycerine (glycerol), 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, the polyethylene glycol and wherein at least two preferably with 3 to 500 repetitive units The mixture of kind.

In a preferred embodiment of the composition, golden (Au) particle has 20 nanometers or smaller, preferably 17 nanometers Or it is smaller, or preferably 15 nanometers or smaller granularity D₅₀。

The present invention also provides the objects comprising layer structure as described above or the layer structure that can be obtained by the above method Body.The object can be those skilled in the art can thus purposes selection any object.The object can be selected from glass plate, cylinder Shape vitreum, the vitreum of irregular shape, ceramic tile, slabstone, metal plate, plank, polymer sheet or film, vase, service plate, Cup, beaker and wherein at least two kinds of combination.

The present invention is illustrated by measurement method, non-limiting embodiment and schematic diagram now.

Measurement method

Unless otherwise specified, test method and embodiment carry out at the standard conditions.Unless otherwise specified, % range is Weight % range.

Substrate:

Screen printing paste is printed on the glass plate having a size of 10 × 7 × 0.3cm.The glass plate is purchased from Leco Glas in

Viscosity:

(Anton is come from using software Rheoplus Version 32V3.40 by cone-plate system Physica MCR 301 Paar) 20 ± 0.1 DEG C at a temperature of using CP 25-1 measurement cone (1 ° of angle) measurement printing composition viscosity.Reaching After temperature 30 seconds, shear rate is through 25 equidistant steps from 1s^-1Rise to 500s^-1, each step respectively keeps constant 30 seconds.500s^-1 Shear rate keep 30 seconds.Shear rate is then down to 1s with 25 as described above equidistant steps^-1.At the end of 30 seconds In 500s^-1Shear rate under measure viscosity.

Wet-film thickness:

In order to measure the thickness degree of hardened layer as described above, the Zeiss5104775 light with 200 times of magnifying powers is used Learn slice microscope.In order to measure, the sample of printing and hardening is placed on sample table and sets 0 position.Then by ten The horizontal line of word directrix and the surface in alignment of the substrate.Then cross-hair is aligned with layer surface and reads measured value.In room It is measured under warm (23 to 25 DEG C).

Transmission electron microscopy (TEM):

Phillips EM420 instrument with 120KV acceleration voltage is used for transmission electron microscopy.One drop is to be checked Sample drop on TEM grid.Then the TEM grid is placed in instrument.It is generating 10 needed for the measurement^-4The high vacuum of Pa During, solvent evaporating completely present in the suspension.Recognizable particle is under measurable degree in microphoto All measure one by one.Statistical estimation of the granularity reported based on gained individual values.

Conductivity:

In order to measure the conductivity of the solution, the Seven with 738 sensor of Inlab (Mettler Toledo) is used GoTM SG3 (comes from Mettler-Toledo).It is calibrated using the aqueous solution with 0.1 and 0.01mol/l KCl concentration.

Glossiness:

It is measured according to EN ISO 2813:1999.Using from TQC Therminport Quality Control The model GL0030 instrument of GmbH.It is measured under angle in 20 ° of incidences/measurement.Substrate is used glass as, at 150 DEG C Layer is after 1 hour dry with a thickness of about 0.3 centimetre.It is calibrated by the polishing filter glass plate being integrated into the instrument.

PH value:

Use Portamess type pH meter (Knick ElektronischeGmbH&Co.KG it) directly surveys Measure the pH of solution.To there is integrated temperature to measure (PT100 electric resistance sensor；Relative to 3mol/l KCL solution) vitreous electricity Pole, model SE200N is dipped into solution to be measured until instruction constant pH.

Silk-screen printing:

By (120 tools per cm of Woven polyester net (with and without structure) 120/34 for being purchased from Sefar AG Have the line of 34 micron diameters) printing (plastic spatula) manually, which is applied directly on glass plate.In each case in room It is printed under mild atmospheric pressure.

It is dry:

The glass plate of printing is introduced to the drying oven for being heated to 150 DEG C (from Thermo Scientific, Typ UT6060 it stops 60 minutes in) and herein.

Embodiment

Embodiment 1:

The manufacture of nano-Au solution:

A it) restores

427 grams of distilled water, 7 grams of K-15 type polyvinylpyrrolidone (coming from AppliChem GmbH, Darmstadt), The solution of 22.3 grams of anhydrous sodium citrates (coming from Merck KGaA, Darmstadt) is in 3 liters of glass beakers in the same of stirring When through 25 minutes be heated to 99-100 DEG C.The glass beaker is covered with clock glass (clock glass).Temperature is monitored by thermometer Degree.Upon reaching that temperature, 21.75% concentration of 46.0 grams of settings to pH=6.9 is added within 15 seconds while being vigorously stirred Gold salt (III) solution (come from Heraeus Precious Metals GmbH).Acutely foaming occurs and color is rapid Become purple from yellow through black.To complete the reaction, then the solution is stirred at 97-98 DEG C other 10 minutes.It should Solution is cooled to room temperature.

B it) precipitates

The dark red solution pass through with 15 to 20 micron hole sizes filter paper (come from Schleicher&Schuell GmbH, Dassel it) filters, is then act through concentrated hydrochloric acid (from Merck KGaA, Darmstadt) and reaches 3.0-3.1/25 DEG C of pH.Then By the way that 5% concentration of aqueous solution of precipitating reagent shown in table 1 is added dropwise, is precipitated receive in the form of black precipitate at room temperature Meter Jin.When solution colour blackening is without leaving blue cast, which terminates.When use mercapto succinic acid as precipitating When agent, need 300 milliliters of precipitation solutions to obtain black precipitate.

C it) purifies

Make black precipitate sedimentation overnight and carefully decants out the limpid brown mother liquor in upper layer.The sediment is then in room temperature It is lower to be washed six times with 100 grams every time acidification distilled water (pH 1.0-1.2).In each washing operation, which is stirred It mixes 10 minutes and settles it at least 3 hours.After 3 hours, it decants out and washs solution.Then with making the pH of the water decanted out exist The distilled water of amount at 25 DEG C for 1.8-2.0 is washed.Washing water has the dry residual quantity at 100 DEG C less than 0.02%. As dried fruit residual quantity is greater than 0.02%, it is necessary to carry out the further washing operation using washing solution or distilled water until reaching 0.02% or lower dry residual quantity (100 DEG C).

D) disperse

Black residue slurrying and by 10% concentration ammonia in 40 grams of deionized waters (2.5-3.0 μ S/cm conductivity) Aqueous solution reaches 4.5-5.0/25 DEG C of pH.This generates peony dispersion, (comes from through filter paper (20-30 micron hole size) Schleicher&Schuell GmbH, Dassel) filtering.The gold content of gained suspension is the 20%Au (weight of ignition residue Method measurement).

Table 1: the mean particle size D 50 in the case where various precipitating reagents

Mercapto succinic acid is purchased from Alfa Aesar GmbH&Co KG, Karlsruhe, and n-acetylcysteine is purchased from Merck KGaA, Darmstadt) and thiodiethanol be purchased from Fluka Chemie GmbH, CH-Buchs.Visually evaluate optics Property.

The raising that can be seen that granularity from the result in table 1 causes the optical property of the composition to change.If granularity is low In 15 nanometers, Lightening composition is obtained.If granularity is higher than 20 nanometers, satin composition is obtained.Therefore it can be controlled by granularity The gloss property of the composition.

Can silk-screen printing paste embodiment

Embodiment I, II and III:

Table 2 list three kinds it is different containing gold can silk-screen printing paste I, II and III ingredient:

Table 2: can silk-screen printing paste exemplary formulations

Component 1-6 is sequentially claimed in the glass dish at least 500 grams volumes.In each case with magnetic stirrer 40 grams of water are evaporated while stirring at 85 DEG C.After complete cooling, be added component 7 and by triple-roller mill (come from EXAKT, Norderstedt, Laborwalzenstuhl) it is homogenized the mixture at room temperature.Carry out twice of homogenizing.

Precipitating reagent mercapto succinic acid sample 1a will then be contained) solution from embodiment 1 or from embodiment I extremely The paste of III is applied in various substrates, is also referred to as applied.Condition in condition, applying mode and heating process is summarised in table 3 In.Table 3 also lists the result of this application.

Table 3: the implementation that various substrate solution and the composition of the invention of paste form apply and heat according to the present invention Example

Embodiment IV and V

Table 4 is listed for the two different containing gold, platinum and palladium of White gold processing (white gold treatment) Can silk-screen printing paste IV and V ingredient:

Table 4: the implementation that various substrate solution and the composition of the invention of paste form apply and heat according to the present invention Example

Component 1-7 shown in table 4 is sequentially claimed in ware appropriate.It is stirred in each case by magnetic stirrer While at 85 DEG C evaporate 279 grams of water.After complete cooling, be added component 8 and by triple-roller mill (come from EXAKT, Norderstedt, Laborwalzenstuhl) it is homogenized the mixture at room temperature.Carry out twice of homogenizing.It Platinum Nanoparticles solution and receives Rice palladium solution is purchased from Strem Chemicals Inc.in Kehl.

In the following,

Fig. 1 shows the schematic diagram of the processing step of method of the invention；

Fig. 2 a shows the schematic diagram of precursor of the invention；

Fig. 2 b shows the schematic diagram of layer structure of the invention；

Fig. 2 c shows the schematic diagram of the layer structure of the invention with additional protective layers；

Fig. 2 d shows the schematic diagram of the object comprising layer structure of the invention；

Fig. 3 shows the electron micrograph of the composition of the invention according to 1 sample a) of embodiment；

Fig. 4 shows the electron micrograph of another composition of the invention according to 1 sample b) of embodiment；

Fig. 5 shows the electron micrograph of another composition of the invention according to 1 sample c) of embodiment；

Fig. 1 schematically shows the step of method of the invention.In step E1 30, provides come from embodiment 1 in a reservoir Composition 6.In step E2 40, being passed through by silk-screen printing using 70Shore rubber scraper has 150 micron mesh sizes Silk screen composition 6 is applied to substrate 4 (for example, glass plate form of size 7*10cm).The wet-film thickness of composition 6 is About 20 microns.Substrate 4 constitutes precursor 12 of the invention with composition 6 together.Substrate 4 and composition 6 one in step E3.50 It rises and is coming from Fisher Scientific, heated 1 hour at 150 DEG C under atmospheric pressure in the hot-air oven of model UT6060. Here, forming layer gold 8 by composition 6 and thus to obtain layer structure 2 of the invention.Can also optionally in step E4 at least by Apply business clear top coat in the layer gold 8 that composition 6 is formed or in entire layer structure 2 (such as automotive coatings Clear coat, such as Profix 2K MS Klarlack CP400 or Profix 2K Klarlack Matt CM10) form Protective layer 10.

Fig. 2 a shows precursor 12, and the substrate 4 by being applied with composition 6 thereon is constituted.Substrate 4 can be such as paper, Glass or ceramics.In this example, substrate 4 is the polypropylene screen with 1 millimeters thick of 20*20cm size.

As by heating precursor 12 shown in Fig. 2 a at 50 DEG C, formed stratiform as shown in figure 2b to shown in Fig. 1 Structure 2.This layer structure 2 is made of substrate 4 and layer gold 8.Layer gold has 1 micron of thickness.

Fig. 2 c shows the layer structure 2 of b according to fig. 2, in addition applies protective layer 10 in layer gold 8.As substitution or separately Outside, protective layer 10 can also be applied to the downside of substrate 4.

Fig. 2 d shows the object 20 being made of the platen 22 for being applied with layer structure 2 thereon.Layer structure 2 includes substrate 4, layer gold 8 and protective layer 10.Layer structure 2 can have and describe identical size and material to Fig. 2 a and 2b.

Fig. 3 shows the transmission electron micrograph of composition 6 of the invention.The composition is equivalent to 1 sample a) of embodiment. The magnifying power of the transmission electron micrograph is 45000.It is clear that the circle to oval gold particle has 1 to 10 The diameter of nanometer, approximately half of particle have the diameter less than 5 nanometers, are equivalent to 4.9 nanometers of D₅₀.10% particle has 2.8 nanometers or smaller diameter, are equivalent to 2.8 nanometers of D₁₀, and 90% particle has 10.1 nanometers or smaller diameter, phase When in 10.1 nanometers of D₉₀.Here, the particle being attached on other particles is considered as single particle.In the freedom of the particle of attachment Side measures diameter.

Fig. 4 display uses the image recorded with the transmission electron microscope (TEM) of the same type described in Fig. 3.Fig. 4 is shown According to the composition 6 of 1 sample b of embodiment.Fig. 4 is obtained with 45000 magnifying power.In figure 4, it can be seen that the gold particle has 3 to 16 nanometers of diameter, approximately half of particle have the diameter less than 10 nanometers, are equivalent to 9.1 nanometers of D₅₀.10% grain Son has 5.5 nanometers or smaller diameter, is equivalent to 5.5 nanometers of D₁₀, and 90% particle has 15.8 nanometers or smaller Diameter is equivalent to 15.8 nanometers of D₉₀.Here, the particle being attached on other particles is considered as single-particle.In the particle of attachment Free side measure diameter.

Fig. 5 display uses the image recorded with the transmission electron microscope of the same type described in Fig. 3.Fig. 5 is with 45000 Magnifying power shows the composition 6 of 1 sample c) of embodiment.In fig. 5 it can be seen that the gold particle has 7 to 40 nanometers of diameter. Approximately half of particle has the diameter less than 27 nanometers, is equivalent to 24.9 nanometers of D₅₀.Here, being attached on other particles Particle is considered as single-particle.Diameter is measured in the free side of the particle of attachment.

From table 1 it follows that the glossiness of composition 6 depends on the granularity of Au particle.Composition 6 in Fig. 3 and 4 is seen Get up light, and the composition 6 in Fig. 5 shows satin.

Such as the routine for transmission electron micrograph, transmission electron microscopy is recorded on the copper mesh with carbon film Photo.

Mark inventory

2 layer structures

4 substrates

6 compositions

8 layer gold

10 protective layers

12 precursors

20 objects

22 platens

30 step E1.

40 step E2.

50 step E3.

60 step E4.

Claims

1. a kind of method for manufacturing layer structure (2), it includes following steps:

E1., a kind of composition (6) is provided, it includes

I.0.1 to the gold particle of the amount of 50 weight %；

Ii. it is supplemented to the polar protic organic solvent of 100 weight %；

Iii. it is less than the water of 5 weight %；With

Iv. lead to sulfydryl-carboxyl compound of formula (I),

SH-R₁-COOH (I)

Wherein

Or at least one salt of this sulfydryl-carboxyl compound；

Wherein these weight % in each case based on the gross mass of composition (6) adds up to 100 weight %,

Wherein the composition (6) has 3 to 8 pH；

E2. composition (6) is applied on substrate (4) to generate precursor (12)；

E3. precursor (12) is heated to 25 to 300 DEG C of temperature to generate layer structure (2).

2. method as described in claim 1, wherein the gold particle has 1 to 25 nanometer of diameter.

3. the method as described in claim 1, wherein selecting the viscous of the composition (6) in the range of 1 to 100000mPas Degree.

4. method according to claim 2, wherein selecting the viscous of the composition (6) in the range of 1 to 100000mPas Degree.

5. the method as described in claim 1, wherein the polar protic organic solvent includes at least polyalcohol of 20 weight %.

6. method according to claim 2, wherein the polar protic organic solvent includes at least polyalcohol of 20 weight %.

7. method as claimed in claim 3, wherein the polar protic organic solvent includes at least polyalcohol of 20 weight %.

8. method as claimed in claim 4, wherein the polar protic organic solvent includes at least polyalcohol of 20 weight %.

9. method as claimed in claim 5, wherein the polyalcohol has 2 to 20 carbon atoms.

10. method as claimed in claim 6, wherein the polyalcohol has 2 to 20 carbon atoms.

11. the method for claim 7, wherein the polyalcohol has 2 to 20 carbon atoms.

12. method according to claim 8, wherein the polyalcohol has 2 to 20 carbon atoms.

13. method as claimed in claim 5, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

14. method as claimed in claim 6, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

15. the method for claim 7, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

16. method according to claim 8, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

17. method as claimed in claim 9, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- the third two Alcohol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- Dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy- 2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, (the hydroxyl first of 1,1,1- tri- Base) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

18. method as claimed in claim 10, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- third Glycol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1, 2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy Base -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, tri- (hydroxyl of 1,1,1- Methyl) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

19. method as claimed in claim 11, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- third Glycol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1, 2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy Base -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, tri- (hydroxyl of 1,1,1- Methyl) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

20. method as claimed in claim 12, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1,3- third Glycol, 1,2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1, 2- dihydroxy benzenes, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy Base -2,5- dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, tri- (hydroxyl of 1,1,1- Methyl) propane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds mixture composition group.

21. method as described in claim 1, wherein polyethylene glycol has 3 to 500 repetitive units.

22. method as described in claim 1, wherein the substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀Alkyl has at least one following property:

E1. the C₁-C₂₀At least one carbon atom of alkyl by least one nitrogen-atoms, oxygen atom, phosphorus atoms, sulphur atom, Hydroxyl, carboxyl, halide, amine, amide, phosphate, sulfate or in which at least two combination replacement；Or

E2. the C₁-C₂₀Alkyl can be by other substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀Hydrocarbon Base replaces or branching；Or

E3. the C₁-C₂₀At least one carbon atom of alkyl has been substituted by aryl or 5-, 6- or 7- member hetero-aromatic ring the case where It is lower by 1,2,3 or 4 nitrogen, oxygen and sulphur atom substitute, wherein the heteroaryl can by halogen atom, hydroxyl, nitro, amino, by Amino, cyano, trifluoromethyl, the alkyl with 1 to 4 carbon atom, the alkoxy with 1 to 4 carbon atom of protection replace.

23. the method as described in claim 22, wherein the substitution, unsubstituted, branching or non-branching, ring-type or polycyclic C₁-C₂₀There are two alkyl tools or all following properties:

24. the method as described in any one of claim 1 to 23, wherein the composition (6) includes to be based on the composition 0.1 to 4 weight % of gross mass meter sulfydryl-carboxyl compound.

25. the method as described in claim 22 or 23 the, wherein sulfydryl-carboxyl compound is selected from L-cysteine, D- half Cystine, γ-L- glutamy-L- cysteinyl glycine, (RS)-N- (2- sulfydryl -1- oxygen propyl group) glycine, mercaptosuccinic Acid, n-acetylcysteine, thiosalicylic acid, dimercaptosuccinic acid, l-methionine, D-Met, thiocarbamide, 2- sulfydryl Propionic acid, thioglycerol, thio-2 acid, cystine, 3- mercapto-propionate, sodium thioglycolate and wherein at least two kinds of mixing The group of object composition.

26. method as claimed in claim 24 the, wherein sulfydryl-carboxyl compound is selected from L-cysteine, half Guang ammonia of D- Acid, γ-L- glutamy-L- cysteinyl glycine, (RS)-N- (2- sulfydryl -1- oxygen propyl group) glycine, mercapto succinic acid, N- Acetyl cysteine, thiosalicylic acid, dimercaptosuccinic acid, l-methionine, D-Met, thiocarbamide, 2 mercaptopropionic acid, Thioglycerol, thio-2 acid, cystine, 3- mercapto-propionate, sodium thioglycolate and wherein at least two kinds of mixture group At group.

27. the method as described in any one of claim 1 to 23, wherein the composition (6) include selected from silver, platinum, palladium, The additional metal for the group that copper, rhodium and wherein at least two kinds of group are combined into.

28. the method as described in any one of claim 1 to 23, wherein the composition (6) further includes surface-active Substance.

29. the method as described in any one of claim 1 to 23, wherein at least in layer structure (2) in additional step E4 A part on apply protective layer (10).

30. the method as described in any one of claim 1 to 23, wherein the substrate (4) is selected from paper, timber, fabric, glass The group that glass, polymer, metal, ceramics, keratinization layer and wherein at least two kinds of group are combined into.

31. the method as described in any one of claim 1 to 23, wherein the substrate (4) has less than 10¹³The conductance of S/cm Rate.

32. the method as described in any one of claim 1 to 23, wherein the application of the composition (6) in step E2. is by brush Son, silk screen, felt pen, fountain pen or nozzle carry out.

33. the precursor (12) of layer structure (2), layered structure (2) can be by as described in any one of the preceding claims Method processing step E1 and E2 obtain.

34. precursor (12) as claimed in claim 33, wherein the precursor (12) has at least one following property:

The thickness of V1.0.1 millimeters to 5 centimetres of substrate (4)；

The thickness of V2.0.1 microns to 70 microns of the composition applied in step E2.；

V3. less than 10¹³The conductivity of the substrate (4) of S/cm；

V4.10^-1S/cm to 10^-8The conductivity for the composition (6) of S/cm applied in step E2..

35. a kind of layer structure (2) can be obtained by the method as described in 2 any one of claims 1 to 3.

36. layer structure (2) as claimed in claim 35, wherein layered structure (2) has at least one following property:

S1. the metal of the thickness in layer structure (2) comprising at least gold of 70 weight % and with 0.05 micron to 1 micron Layer；

S2. less than 10¹³The conductivity of S/cm；

The glossiness of S3.500 to 1300GU；

The density of S4.10 to 20kg/l.

37. a kind of composition (6), it includes:

The gold particle of the amount of z1.0.1 to 50 weight %；

The water of z2.0 to 5 weight %；

Z3. it is supplemented to the polar protic organic solvent of 100 weight %；

The composition (6) includes at least one annexing ingredient, is selected from:

Z4. based on the gross mass of composition (6), the polyvinylpyrrolidone of the amount of 0 to 10 weight %；

Z5. based on the gross mass of composition (6), the polyalcohol of the amount of 0 to 90 weight %；

Wherein these weight % in each case based on the gross mass of composition (6) adds up to 100 weight %.

38. composition (6) as claimed in claim 37, wherein the polyalcohol is selected from 1,2- ethylene glycol, 1,2-PD, 1, 2,3- glycerine, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 2,3- butanediol, 1,2,3- butantriol, 1,2- dihydroxy Base benzene, 1,3- dihydroxy benzenes, 1,4- dihydroxy benzenes, 1,2,3- trihydroxy benzene, 1,2,4- trihydroxy benzene, 1,4- dihydroxy -2,5- Dinitrobenzene, L- adrenaline, monosaccharide, disaccharides, the monosaccharide mixed with liquid polyol or disaccharides, 1,1,1- tri- (methylol) third The group of alkane, 2,2- dimethyl propylene -1,3- glycol, polyethylene glycol and wherein at least two kinds of mixture composition.

39. the composition (6) as described in claim 38, wherein polyethylene glycol has 3 to 500 repetitive units.

40. the composition (6) as described in claim 37 or 38, wherein the gold particle has 20 nanometers or smaller granularity D₅₀。

41. a kind of object (20), it includes as described in claim 35 or 36 or can be by such as 2 any one of claims 1 to 3 The layer structure (2) that the method obtains.